EP3470467B1 - Colorants methine pour colorer les plastiques - Google Patents

Colorants methine pour colorer les plastiques Download PDF

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EP3470467B1
EP3470467B1 EP18197034.4A EP18197034A EP3470467B1 EP 3470467 B1 EP3470467 B1 EP 3470467B1 EP 18197034 A EP18197034 A EP 18197034A EP 3470467 B1 EP3470467 B1 EP 3470467B1
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hydrogen
formula
chlorine
methyl
plastic
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EP3470467A1 (fr
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Hans-Ulrich Borst
Frank Linke
Stephan Michaelis
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present invention relates to new methine dyes, processes for their production and their use for coloring plastics.
  • Pigments are known from the prior art which are suitable for coloring plastics in yellow shades.
  • DE-A 3543512 A1 describes pigments based on azo lakes ( Bayplast® Yellow G) which can be used to color polyamide in yellow shades.
  • Pigment Yellow 192 (C.I. 507300) to achieve yellow plastic coloring has also been known for a long time.
  • pigments mentioned have good thermal stability, transparent coloring of plastics cannot be achieved with them. In addition, pigments can impair the mechanical properties of the polymers. It is known from the prior art to use soluble dyes (solvent dyes) to transparently color plastics in yellow shades. The mechanical properties of the polymers are generally not adversely affected by dyes.
  • Known soluble yellow dyes are, for example, Solvent Yellow 114 (CI 47020) from the class of quinophthalone dyes, Solvent Yellow 160:1 (CI 55165) from the class of coumarin dyes and Solvent Yellow 179 (N-2-((4-cyclohexyl)phenoxy)ethyl -N-ethyl-4-(2,2-dicyanoethenyl)-3-methylaniline) and Solvent Yellow 93 (C.I. 48160), both from the class of methine dyes.
  • Solvent Yellow 114 CI 47020
  • Solvent Yellow 160:1 CI 55165
  • Solvent Yellow 179 N-2-((4-cyclohexyl)phenoxy)ethyl -N-ethyl-4-(2,2-dicyanoethenyl)-3-methylaniline
  • Solvent Yellow 93 C.I. 48160
  • photopolymer compositions which have a photopolymerizable component and a photoinitiator system, the photoinitiator system containing a chain-substituted cyanine dye.
  • the dyes of the formula (I) can exist as stereoisomers.
  • the formula (I) includes in particular the following four E and Z isomers of the formulas (la) to (Id): in which the substituents R 1 to R 7 each have the general and preferred meanings given for formula (I).
  • the present invention relates to methine dyes of the formula (Ia) in which the substituents R 1 to R 7 have the general and preferred meanings given for formula (I).
  • the dyes of the formula (I) according to the invention can be used to give plastics, in particular polyamides, yellow to orange colorations which are distinguished by improved lightfastness and improved thermal stability compared to the yellow dyes known for this purpose.
  • the dyes according to the invention surprisingly also have improved color strength compared to the known dyes.
  • a further subject of the present invention is the use of the dyes of the formula (I) according to the invention for bulk coloring of plastics.
  • the dyes according to the invention can be used individually or in any mixture with one another.
  • Mass coloring is understood to mean in particular processes in which the dye is incorporated into the molten plastic mass, eg with the aid of an extruder, or in which the dye is already added to the starting components for the production of the plastic, eg monomers before polymerization.
  • Particularly preferred plastics are thermoplastics, for example vinyl polymers, polyesters, polyamides and polyolefins, in particular polyethylene and polypropylene, polycarbonates and polyamide.
  • Polyamides, in particular polyamide 6.6 and polyamide 6, are very particularly preferred.
  • Polyamide 6.6 is usually made from hexamethylenediamine (HMD) and adipic acid. It is formed by polycondensation with elimination of water.
  • HMD hexamethylenediamine
  • adipic acid adipic acid
  • Polyamide 6 can be obtained by ring-opening polymerization of ⁇ -caprolactam with water as the initiator.
  • Suitable vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate, polyvinyl chloride and others.
  • polyesters examples include polyethylene terephthalates, polycarbonates and cellulose esters.
  • the plastics to be colored can be present individually or in mixtures with one another, as plastic masses or melts.
  • the dyes (I) according to the invention are preferably used in finely divided form, it being possible for dispersants to be used, but this does not have to be the case.
  • the dyes (I) according to the invention can be used, for example, directly in the plastics production process after polymerization has taken place.
  • at least one Dye (I) according to the invention is mixed or ground dry with the plastic granules and this mixture is plasticized and homogenized, for example on mixing rollers or in screws.
  • the dyes (I) according to the invention can also be added to the molten mass and distributed homogeneously by stirring.
  • the material precolored in this way can then be further processed in the usual manner, for example by spinning to form bristles, threads, etc., or by extrusion or by injection molding to form molded parts.
  • the dyes (I) are resistant to polymerization catalysts, in particular peroxides, it is also possible to add the dyes (I) according to the invention to the monomeric starting materials for the production of plastics, e.g. B. of polymethyl methacrylate (PMMA) and then to polymerize in the presence of polymerization catalysts.
  • the dye is preferably dissolved in the monomeric components or intimately mixed with them.
  • the dyes of the formula (I) according to the invention are preferably used for coloring the plastics mentioned, in particular polyamide, in amounts of from 0.0001 to 1% by weight, in particular from 0.01 to 0.5% by weight, based on the amount of polymer used.
  • pigments that are insoluble in the polymers such as titanium dioxide
  • corresponding valuable opaque colors can be obtained.
  • Titanium dioxide can be used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the amount of polymer.
  • the present invention also relates to a process for bulk coloring of plastics, in which at least one dye of the formula (I) is dry-mixed or ground with at least one plastic, preferably in granular form, and this mixture is plasticized and homogenized, for example on mixing rollers or in screws.
  • the dyes (I) according to the invention can also be added to the molten mass and distributed homogeneously by stirring. It is also possible to add the dyes (I) according to the invention to the monomeric starting components during the production of plastics and then to polymerize them.
  • the material precolored in this way can then be further processed in the usual manner, e.g. by spinning to form bristles, threads, etc., or by extrusion or injection molding to form molded parts.
  • the process according to the invention gives transparent or opaque brilliant yellow dyeings with very good heat and light stability.
  • the present invention also provides a process for preparing the dyes of the formula (I) according to the invention.
  • the aldehydes of the formula (II) can exist as stereoisomers.
  • the formula (II) includes the two possible E and Z forms.
  • the process for preparing the dyes (I) according to the invention by reacting the aldehydes of the formula (II) with the benzothiazole derivatives of the formula (III) can be carried out in a manner known per se.
  • the process for preparing the dyes (I) according to the invention is generally carried out at a temperature in the range from -10 to 180.degree. C., preferably from 0 to 100.degree. C. and particularly preferably from 10 to 90.degree.
  • the process for preparing the dyes (I) according to the invention is generally carried out at a pressure of from 900 to 1100 hPa, preferably at normal pressure.
  • the process for preparing the dyes (I) according to the invention can be carried out in the presence of at least one solvent.
  • Suitable solvents are, for example, those from the alcohol and formamide series.
  • the process for preparing the dyes (I) according to the invention is preferably carried out in the presence of at least one alcohol from the group consisting of methanol, ethanol and propanol and/or at least one formamide from the group consisting of dimethylformamide and diethylformamide, particularly preferably in the presence of methanol and/or dimethylformamide carried out.
  • the process for preparing the dyes (I) according to the invention is carried out in the presence of at least one base.
  • suitable bases are alkali metal hydroxides and alkali metal alcoholates. Preference is given to using lithium hydroxide, sodium hydroxide, potassium hydroxide and/or potassium tert-butylate, particularly preferably sodium hydroxide and/or potassium tert-butylate.
  • the process for preparing the dyes (I) according to the invention is carried out such that the aldehyde (II) is initially initially taken and the benzothiazole derivative (III) is added and, after the reaction has taken place, the compounds of the formula (I) are isolated.
  • the isolation can be carried out by customary methods, preferably by filtration.
  • the reaction product obtained can optionally be worked up by further process steps such as washing and drying.
  • the process is generally carried out using from 0.8 to 1.5 mol of benzothiazole derivative (III) per mole of aldehyde (II). Preference is given to using from 0.9 to 1.1 mol of benzothiazole derivative (III) per mole of aldehyde (II), and it is particularly preferred to use 1 mol of benzothiazole derivative (III) per mole of aldehyde (II).
  • Benzthiazole derivatives of the formula (III) are known and can be obtained, for example, as commercial products from Alfa Acer.
  • reaction in stage a) is carried out by initially introducing the indole derivative of the general formula (IV) and adding the alkylating agent, if appropriate in the presence of a solvent.
  • the first stage a) of the reaction is generally carried out at a temperature in the range between 10 and 80°C, preferably from 20 to 70°C and particularly preferably from 30 to 60°C.
  • the reaction in stage a) is generally carried out at a pressure of from 900 to 1100 hPa, preferably at normal pressure.
  • the reaction in stage a) can be carried out in the presence of at least one solvent. Suitable solvents are, for example, those from the alcohol and water series.
  • the reaction in stage a) is preferably carried out in the presence of water as the solvent.
  • alkylating reagents are suitable as alkylating reagents (see e.g. BK Schwetlick, Organikum, VEB Deutscher Verlag dermaschineen, Berlin, 15th edition 1977, page 260, 253, 674 ), such as dimethyl sulfate, methyl iodide or diazomethane.
  • dimethyl sulfate is preferred.
  • At least one mole of alkylating reagent is used per mole of indole derivative.
  • higher molar amounts are also used.
  • the intermediate produced in stage a) can be isolated by customary methods, for example by filtration.
  • the intermediate product prepared in stage a) is preferably reacted further directly in the subsequent stage b) without isolation.
  • the reaction in stage b) is carried out by initially introducing the alkylated compound from the first stage a) in the form of the reaction solution obtained and adding the formylation reagent, if appropriate in the presence of at least one solvent, and then adding the aldehyde of the formula ( II), optionally precipitating by adding a suitable amount of a suitable precipitating agent, and then isolating the aldehyde of the formula (II) by customary methods, for example by filtration.
  • the reaction in stage b) is generally carried out at a temperature in the range between 10 and 80°C, preferably from 20 to 70°C and particularly preferably from 30 to 60°C.
  • the reaction in stage b) is generally carried out at a pressure of 900 to 1100 hPa, preferably at normal pressure.
  • the reaction in stage b) can be carried out in the presence of at least one solvent.
  • suitable solvents are formamides. Dimethylformamide and diethylformamide are preferred, and the use of dimethylformamide is particularly preferred. When using dimethylformamide, it is particularly preferred to use this in excess, the dimethylformamide then serving both as a formylation reagent and as a solvent.
  • a mixture of at least one formamide and at least one phosphoric acid chloride is generally used as the formylation reagent in stage b).
  • Preferred formamides are dimethylformamide, diethylformamide and dibutylformamide.
  • Preferred phosphoric acid chloride is phosphorus oxychloride.
  • a mixture of dimethylformamide and phosphorus oxychloride is particularly preferably used as the formylation reagent.
  • At least one mole of formylation reagent is used per mole of alkylated compound from stage 1, preferably 1.1 to 1.5 mol and particularly preferably 1.1 to 1 mol.
  • Suitable precipitating agents are, for example, alcohols such as methanol and/or ethanol.
  • the precipitating agent used is preferably methanol and/or ethanol, in particular methanol.
  • the diazotization reaction is generally carried out by charging the aniline derivative and adding the diazotization reagent at a temperature ranging from 0 to 10°C under normal pressure in an aqueous medium.
  • any suitable diazotization reagent can be used as the diazotization reagent.
  • the use of an aqueous sodium nitrite solution is preferred.
  • the diazotization reagent is used in an amount of at least two moles, based on the aniline derivative (V).
  • the ring-closure reaction with the ketone of the formula (VI) is carried out in a manner known per se in a one-pot reaction by reducing the diazonium salt of the aniline derivative (V) to the hydrazone and reacting the hydrazone with the ketone of the general formula ( VI) reacts, preferably at a temperature in the range from 40 to 100° C., preferably in aqueous solution, and then the indole derivative of the formula (IV) is isolated and washed by customary methods, preferably filtration.
  • aniline derivatives of the formula (V) and the ketones of the formula (VI) are known and can be obtained as commercial products, for example from Alfa Acer or Sigma-Aldrich.
  • the diazotization solution prepared in step a) was added over the course of about 30 minutes, the pH being kept at about 6.5 by adding 100 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was then stirred at a temperature of 40° C. for about 1 hour. Thereafter, 560 g of 96% sulfuric acid and then 86.1 g of methyl isopropyl ketone were added dropwise. The reaction mixture was heated to 70°C and stirred for about 4 hours.
  • reaction mixture was then heated to 80° C. and stirred again for about 4 hours.
  • the reaction mixture was then cooled to 25° C. and adjusted to a pH of 6.5 with about 800 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was stirred for 30 minutes and then the reaction product was isolated on a suction filter and washed with 2 liters of water.
  • the water-moist presscake of the ring closure product from stage b) was introduced into 1200 g of water.
  • a pH of 10 was then set with about 70 g of a 40% aqueous sodium hydroxide solution.
  • 325 g of dimethyl sulfate were added dropwise over the course of 1 hour, while the pH was kept at about 8.5 by adding 200 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was warmed to 40°C and stirred for ca. 5 hours.
  • the reaction mixture was then heated to 60° C. and stirred again for 1 hour.
  • the reaction mixture was then left to phase separate over 1 hour. Then the aqueous phase was separated. Residual water was removed from the organic phase in vacuo at 80° C.
  • the diazotization was prepared as described in Example 8a), but instead of 270 g of 30% hydrochloric acid and 139.9 g of p-aminobenzoic acid, 268 g of 30% hydrochloric acid and 127.6 g of 4-chloroaniline were used.
  • the hydrazone was prepared and the ring closed analogously to Example 8b), but the diazotization solution from Step 9a) was used.
  • the water-moist presscake of the ring closure product from stage b) was introduced into 1200 g of water.
  • a pH of 10 was then set with about 5 g of a 40% aqueous sodium hydroxide solution.
  • 153 g of dimethyl sulfate were added dropwise over the course of 1 hour, while the pH was kept at about 8.5 by adding 90 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was warmed to 40°C and stirred for ca. 5 hours.
  • the reaction mixture was then heated to 60° C. and stirred again for 1 hour.
  • the reaction mixture was then left to stand within 1 hour phase separation took place. Then the aqueous phase was separated. Residual water was removed from the organic phase in vacuo at 80° C.
  • the diazotization was prepared as indicated in Example 8a). However, instead of 270 g of 30% hydrochloric acid and 139.9 g of p-aminobenzoic acid, 375 g of 30% hydrochloric acid and 155.5 g of 3-fluoroaniline were used.
  • the diazotization solution prepared in step a) was added over the course of about 30 minutes, the pH being kept at about 6.5 by adding 140 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was then stirred at a temperature of 40° C. for about 1 hour. Thereafter, 776 g of 96% strength sulfuric acid and then 120.4 g of methyl isopropyl ketone were added dropwise.
  • the reaction mixture was heated to 70°C and stirred for about 4 hours.
  • reaction mixture was then heated to 80° C. and stirred again for about 4 hours.
  • the reaction mixture was then cooled to 25° C. and adjusted to a pH of 6.5 with about 1150 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was stirred for 30 minutes and then the reaction product was isolated on a suction filter and washed with 2 liters of water.
  • the water-moist presscake of the ring closure product from stage b) was introduced into 1200 g of water.
  • a pH of 10 was then adjusted with 10 g of a 40% aqueous sodium hydroxide solution.
  • 194 g of dimethyl sulfate were added dropwise over the course of 1 hour, while the pH was kept at about 8.5 by adding 120 g of a 40% strength aqueous sodium hydroxide solution.
  • the reaction mixture was warmed to 40°C and stirred for ca. 5 hours.
  • the reaction mixture was then heated to 60° C. and stirred again for 1 hour.
  • the reaction mixture was then left to phase separate over 1 hour. Then the aqueous phase was separated. Residual water was removed from the organic phase in vacuo at 80° C.
  • the diazotization was prepared as indicated in Example 8a). However, instead of 270 g of 30% hydrochloric acid and 139.9 g of p-aminobenzoic acid, 375 g of 30% hydrochloric acid and 162.0 g of 3,4-dichloroaniline were used.
  • the hydrazone was prepared and the ring closed analogously to Example 10b), but the diazotization solution from Step 11a) was used.
  • the aldehyde was prepared and worked up as indicated in example 10c), but the water-moist presscake of the ring-closure product from stage 11b) was used.
  • the extinction of a solution of the respective sample in 1-methoxy-2-propyl acetate is measured in a cuvette with a path length of 1 cm, the concentration of the solution being chosen such that the observed extinction value is about 1 at the absorption maximum.
  • the determined value is then converted to a concentration of 1 percent by weight, which results in the E 1/1 value.
  • the heat stability of the plastic granules obtained was tested in accordance with DIN EN 12877-2 ("Determination of the resistance of the color to heat when processing colorants in plastics") (Method A) on an injection molding machine.
  • a sample was prepared at 240°C with a residence time in the screw of 2.5 minutes.
  • the samples to be determined which were produced with a residence time of 5 minutes and temperatures of 240-320° C., were coloristically evaluated against this standard sample.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coloring (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (14)

  1. Colorant de formule (I)
    Figure imgb0020
     dans laquelle
    R1 représente hydrogène, fluor, chlore, COOH ou COOR8 ,
    R2 représente hydrogène, fluor, chlore, C1-C4-alkyle ou CF3,
    R3 représente hydrogène, fluor, chlore, COOR9 ou CN, R4 représente C1-C4-alkyle ou phényle,
    R5 et R6 représentent indépendamment l'un de l'autre C1-C4-alkyle,
    R7 représente hydrogène, fluor, chlore, C1-C4-alkyle ou CF3,
    R8 représente C1-C4-alkyle et
    R9 représente C1-C4-alkyle,
    à la condition que R1 et R3 ne représentent pas simultanément hydrogène.
  2. Colorant selon la revendication 1, caractérisé en ce que dans la formule (I)
    R1 représente hydrogène, chlore, COOH ou COOCH3,
    R2 représente hydrogène, chlore, méthyle, éthyle, n-propyle, isopropyle ou CF3,
    R3 représente hydrogène, fluor, chlore, COOCH3 ou CN,
    R4 représente méthyle ou phényle,
    R5 et R6 représentent méthyle et
    R7 représente hydrogène, chlore, méthyle, éthyle, n-propyle, isopropyle ou CF3,
    à la condition que R1 et R3 ne représentent pas simultanément hydrogène.
  3. Colorant selon la revendication 1 ou 2, caractérisé en ce que dans la formule (I)
    R1 représente hydrogène, chlore ou COOCH3,
    R2 représente hydrogène ou méthyle,
    R3 représente hydrogène, fluor ou chlore,
    R4 représente méthyle,
    R5 et R6 représentent méthyle et
    R7 représente hydrogène, chlore ou méthyle
    à la condition que R1 et R3 ne représentent pas simultanément hydrogène.
  4. Utilisation d'au moins un colorant selon au moins l'une des revendications 1 à 3 pour la peinture dans la masse de matières plastiques.
  5. Utilisation selon la revendication 4, caractérisée en ce qu'il s'agit d'au moins une matière plastique de la série des polymères de vinyle, des polyesters, les polyoléfines, des polycarbonates et des polyamides.
  6. Utilisation selon au moins l'une des revendications 4 et 5, caractérisée en ce que la matière plastique est un polyamide 6 et/ou un polyamide 6.6.
  7. Utilisation selon au moins l'une des revendications 4 à 6, caractérisée en ce que le colorant est utilisé en une quantité de 0,0001 à 1 pour cent en poids, en particulier de 0,01 à 0,5 pour cent en poids, par rapport à la quantité de matière plastique.
  8. Procédé pour la teinture dans la masse de matières plastiques, caractérisé en ce qu'au moins un colorant selon au moins l'une des revendications 1 à 3 est mélangé ou broyé à sec avec au moins une matière plastique, de préférence sous forme de granulés et ce mélange est fondu et homogénéisé.
  9. Procédé pour la teinture dans la masse de matières plastiques, caractérisé en ce qu'au moins un colorant selon au moins l'une des revendications 1 à 3 est ajouté à une masse de matière plastique fondue, contenant au moins une matière plastique et celle-ci est ensuite homogénéisée.
  10. Procédé pour la teinture dans la masse de matières plastiques, caractérisé en ce qu'au moins un colorant selon au moins l'une des revendications 1 à 3 est mélangé avec les composants de départ monomériques pour la préparation d'au moins une matière plastique et le mélange est par la suite polymérisé.
  11. Procédé pour la teinture dans la masse de poly(méthacrylate de méthyle) (PMMA), caractérisé en ce qu'au moins un colorant selon au moins l'une des revendications 1 à 3 est mélangé avec au moins un monomère d'ester méthylique d'acide méthacrylique ou est dissous dans celui-ci et ce mélange ou cette solution est ensuite polymérisé(e) en présence d'au moins un catalyseur de polymérisation.
  12. Composition de matière plastique, en particulier composition de polyamide ou poly(méthacrylate de méthyle), caractérisée en ce qu'elle contient au moins un colorant selon au moins l'une des revendications 1 à 3.
  13. Pièces moulées, caractérisées en ce qu'elles contiennent au moins une composition de matière plastique selon la revendication 12.
  14. Procédé pour la préparation d'un colorant selon la revendication 1, caractérisé en ce qu'au moins un aldéhyde de formule (II)
    Figure imgb0021
     dans laquelle
    R1, R3, R4, R5 et R6 possèdent les significations indiquées dans la revendication 1,
    est transformé avec au moins un dérivé de benzothiazole de formule (III)
    Figure imgb0022
    dans laquelle
    R2 et R7 possèdent les significations indiquées dans la revendication 1.
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